N-(O,S-Dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters

ABSTRACT

N-(O,S-dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters of the general formula acid alkyl esters of the general formula   in which X is oxygen of R, R&#39;&#39; and R&#39;&#39;&#39;&#39; each independently is lower alkyl with 1 to 6 carbon atoms, WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent [191 Hoffmann et al.

Sept. 2, 1975 N-( O,S-DIALKYL(TH1ONO )-THIOLPHOS- PHORYLHMINOFORMIC ACID ALKYL ESTERS Inventors: Hellmut Hoffmann,

WuppertaLElberfeld; Ingeborg Hammann, Cologne, both of Germany Bayer Aktiengesellschaft, Leverkusen, Germany Filed: Mar. 31, 1972 Appl. No.: 240,282

Assignee:

Foreign Application Priority Data Apr. 6, l97l Germany 2116690 US. Cl. 260/950; 260/968; 424/217 Int. Cl.'- C07F 9/24; AOlN 9/36 Field of Search 260/950, 968

References Cited UNITED STATES PATENTS 7/1958 Melamed 260/950 X Plillltll' E.\'aminer-Anton H. Sutton Attorney, Agent, or Firm-Burgess, Dinklage & Sprung 57 ABSTRACT N-(O,S-dialkyl(thiono)-thiolphosphoryl)-iminoformic acid alkyl esters of the general formula acid alkyl esters of the general formula.

which possess insecticidal and acaricidal properties.

10 Claims, No Drawings N-( ()a -DIALKYL( THIONO )-TI*IIOLPH()S- PHORYL)-IMINOFORMIC ACID ALKYL ESTERS The present invention relates to and has for its objects the provision of particular ne N-(O,S-dialkyl (thiono)-thiolphosphoryl)-iminoformic acid alkyl esters which possess insecticidal and acaricidal properties. active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such'compounds in a new way es- (Ila) pecially for combating pests. e.g. insects and acarids. with other and further objects becoming apparent from a study of the within specification and accompanying examples. I

It is known from German Published Specification DAS 1,195,750 that N-(0,0-dialkylphosphoryl)- imino-dithiocarbonic acid dialkyl esters. such as N- (0,0-diethylphosphoryl )-imino-dithiocarbonic acid diethyl ester (Compound A) have insecticidal properties.

The present invention provides N-(O.S-dialkyl(thionothiolphosphoryl) iminoformic acid alkyl esters of the formula in which X is oxygen or sulfur, and R, R and R" each independently is lower alkyl with l to 6 carbon atoms.

Preferably R and R each is a straight chain or branched lower alkyl with l to 4 carbon atoms, such as methyl, ethyl, npropyl, isopropyl, n-butyl. isobutyl, sec.-butyl or tert.-butyl, and R" is a lower alkyl with l-3 carbon atoms.

Surprisingly, the compounds according to the invention have a rather better insecticidal, especially sys temic and acaricidal activity than the known N-(0.0- dialkylphosphoryl)-iminodithio carbonic acid dialkyl esters of analogous constitution and the same direction of activity. They therefore represent a genuine enrichment of the art.

The invention also provides a process for the produc tion of a N-(O.S-dialkyl-(thiono)-thiolph0sphoryl- )imino formic acid alkyl esters of the formula (I) in which an O,S-dialkyl-(thiono)-thiolphosphoric acid ester amide of the formula in which X, R and R have the meanings stated above,

i 2 is reacted with an ortho-formic acid alkyl ester of the formula in which i R has the meaning stated above.

If O.S-dimethylthiolphosphoric acid ester amide and ortho-formic acid ethyl ester are used as starting materials. the reaction course can be represented by the following formula scheme:

lllla) (I) Examples of the compounds of formulae (II) and (III) include: O.S-dimethyl-. ().S-diethyl-. O.S-di-npropyl-. O.S-di-isopropyl-. ().S-di-nbutyl-. O.S-di-sec.- butyl-, O.S-di-isobutyl-, O.S-ditert.-but \'l'. O-mcthyl- S-ethyl-, O-methyl-S-n-propyL, O-methyl-S-isopropyl- O-methyl-S-n-butyl-. O-methyl-S-iso-butyl-. O-methylS-tert.-butyl-. Omcthyl-S-sec.-butyl-. O-cthyl-S-m propyl-, O-ethyl-S-isopropyln O-ethyl-S-n-lmtyL, O- ethyl-S-sec.-btuyl. O-ethyl-S-iso-butyl-. O-ethyl-S- tcrt.-butyl-, O-npropyl-S-n-butyl-, O-n-propyl-S-sec.- butyl-. O-n-propyl-S-tert-butyl-. O-ll])I'O}'I \'lS-i$0 lwutyl, O-iso-propyl-S-n-butyl-, O-iso-propyl-S-sec. butyland O-iso-propyl-S-tert.-butyl-thiolophosphoric acid ester amide and the corresponding thiono analogues, and the methyl. ethyl or propyl esters of orthoformic acid.

The compounds of formula (II) are known from the literature and can be made by known methods. e.g. German Published Specification DAS 1216.835 and Dutch Patent Specification No. 69 H925. The compounds of formula (III) and methods for their preparation are also known.

The process according to the present invention can be carried out with the use of a solvent, which term includes a mere diluent. Preferably, however, no solvent is used for the reaction.

If desired an acid catalyst may be used. for example p-toluene-sulfonic acid.

The reaction temperatures can be varied over a wide range. In general, the reaction is carried out at about l()0-2()()C, preferably about l4()l6()C.

In general, the reaction is carried out at normal pressure.

In carrying out the process. the reactants are preferably brought together in the absence of any solvent. the ortho-formic acid ester being usually used in a 10-20% excess. The mixture is boiled under reflux for several hours, in the course of which the alcohol which forms is distilled off. The residue is distilled.

The compounds of the invention are in most cases i obtained as colorless or slightly yellow oils which can mostly be distilled without decomposition. If not, they can be freed from volatile impurities by .slight distilla tion, that is, longer heating to moderately elevated temperatures under reduced pressure. The refractive index is particularly useful for theircharacterization.

As indicated above. the compounds of the invention are distinguished by outstanding insecticidal and acaricidal effectiveness against crop pests. hygiene pests and pests of stored products. They have a good activity against both sucking and biting insects and mites (Acarina). They are at the same time only slightly phyto toxic and have a five-fold to 10-fold lower toxicity to warm-blooded animals than do the compounds from which they are derived. I '1 The compounds of the invention can-the-reforebe used successfully as pesticides in crop protectioniand the protection of stored products as well as in the field of hygiene. 1

To the sucking insects contemplated herein there belong, in the main. aphids (Aphidae) such as the green peach aphid (Nlvzus pursicuu). the bean aphid (Durull's fir/nu). the bird cherry aphid (Rlmpuloxiplumi pm). the

pea aphid (Mm-rm'ip/mm pisi) and the potato aphid (Mucrm-ip/mm salami/Mil). the currant gall aphid (Crypmmyzus kmisv/u'lfi). the rosy apple aphid (SappuphLs' nzuli). the mealy plum aphid (Hyulupu'rus urumlinis) and the cherry black-fly (Mygm' ('w'usi); in addition. scales and mealybugs (Coccina). for example the. oleander scale (Avpidiums lu'dm-uc) and the soft scale (Lr't'u'nimn hcxpvrir/mn) as well as the grape mealybug (Pscmloummmurilimm' thrips ('lhysanoptera such 11Slhl't'ilIUl/IITIJXjtHlUI'U/iS. and bugs. for example the beet bug (Pies-um qumlrulu). the red cotton bug (Dyst/CIL'IM' imz'rmr'diux). the bed bug ((imex lcctulm'ius). the assassin bug ('R/mz/nius pro/Arm) and Chagas' bug ('Triumnm ill/ZiVIUIIS) and, further. cicadas. such as ljuxcclix hiluhumxand IVOp/zolelrir-bipmu'1ulux; and the like. i i I In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars ('Lepidoptera) 'such as.the diamond-back moth (Plural/u muculrpwznis the gypsy moth (L \mumriu dispur). the browntail moth (Eupruclis ('/H \S()II'/ll)(tl) and tent caterpillar (Mulucosuma m'usl-riu); further. the cabbage moth (Ma/21mm: [)I'UAZS'IIUL) and the cutworm Agmris .s'cg etmiz the large white butterfly (Pieris brus- .viulc). the small winter moth (C/zainmmhiu bruimllu). the green oak tortrix moth Torn-ix ririzlunu). the fall armyworm (Laplrvgmu ji'ugipw'du) and cotton worm (Pl'mle'niu Iimru). the ermine moth (Hyponmneulu [)(ltlt'l/(l). the Mediterranean flour moth (Iip/zestia kl'l'hmic/la) and greater was moth (Galleria nwllonellu); and the like.

Also to be classe d'with the biting insects contemplated herein are beetles (Coleoptera). for example the granary weevil (.S'iIop/zilux gramu'ius Culmulm grunuriu). the Colorado beetle (Leptinolursu decentlineuta). the dock beetle ((iusti'oplrnw riridul u). the mustard beetle (Plzuedon (och/curiae). the blossom beetle (Mcligellms ueneux). the raspberry beetle (Bylurus IOHMHIUSHS). the bean weevil (Bruc/u'zlizmv Ac'un- !/i'u.i'celiz1cs obreclus the leathcr'bee tle ([)ermestesfi'ischi). the k'hapra beetle (Tmgozlerma granurium); the

flour beetle (Trilmlium custaneum). the northern corn billbug (Calandra orSitophilus zcamais). the drugstore beetle (Siege/2mm puniceum). the yellow mealworm (Tenebrio n'zolimr) and the saw-toothed grain beetle 0r \'zueplzilus .s'urimlmensis). and also species living in the soil. for example wireworms (Agriurs spec.) and larvae of the cockchafer (Melolont/za meIOlonr/zu); cockroaches. such as the German. cockroach"(B1auelIa germunica). American cockroach (Peripluneru antericzmu). Madeira cockroach (Lem-oplzaeu orR/rvpurobia HItItIL'I'UL). oriental cockroach (Blallu uriwitulir). the giant COCkl'OZlCh (Blilhll'llS .qiganleus and the black giant cockroach (Blul u'rux-ji (.i') l'as well as-Henxc/ znutedz'niu flariviml; further-,'Orthoptera. for example the house cricket (Ac/zeta clunms'licus); termites such as the eastern subterranean termite (Reticulitermas'.fluripasd and Hy'menoptera such as ants. forexample the gardenrant (Lasius nigenh and the like.

The Diptera contemplated herein comprise essentially the flies. such as the vinegar fly (Drosop/zilu "161th nogaster). the Mediterranean fruit fly (Qln utitis cupitum). the house fly (Muscu domexticu). the little house fly (Fumziu canic'uluris). the black blow .fly (P/mrmiu rvginu) and bluebottle fly (Culliplmra (I' \I/lI'UCP/ltlld) as well as the stable fly (Smmarys c'ulcirrans); further. gnats. for example mosquitoes such as the yellow fever mosquito (Aedes uegypri). the northern house mosquito (Cu/ex pipiwis) and the malaria mosquito (Anopheles .stcphcnsi); and the like.

With the mites (Acari) contemplated herein there are classed. in particular. the spider mites (Tetranyehidae) such as the two-spotted spider mite (Tetrunyclzus lelurills TLIIUII \'(']IIIS all/mule or Tbrrmrrclum urlic'ue) and the European red mite (Puratetrimyclzus pilosus Punmrvc/ms ulnu'). gall mites. for example the black currant gall mite (Eriop/rves ribis) and tarsonerriids. for example the broad mite (Hemimrsonemus lams) and the cyclamen mite (Tursunemuls' palliilm); finally, ticks such as the relapsing fever tiek.(()rni-- I/wzlorus muubura); and the like. 1

When applied against hygiene pests and pests of stored products. particularly flies and mosquitoes. the compounds of the invention. are also distinguished by an outstanding residual activity on wood and clay. as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized. if desired. in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders. i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier'vchicles such as gases. solutions. emulsions. suspensions, emulsifiable concentrates, spray powders, pastes. soluble powders, dusting agents, granules, etc. These are prepared in known mannenfor instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants. e'.g. conventional pesticide I surface-active agents, including emulsifying agents "and/ or dispersing agents. whereby. forexample, in the case where water is used as diluent.' organic solvents be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including amine. etc.), amides (e.g. dimethyl formamidc. ctc.). sulfoxides (e.g. dime'thyl'sulfoxide. ctc.). acetonitrile. kctones (cg. acetone. methyl ethyl ketone. methyl isobutyl ketonc. cyclt'ihexanone. "ete'); "and/or water; as well as inert dispersible. finely divided solid carriers. such as ground natural minerals (e.g. kaolins. clays. alumina. silica, chalk', i.e. calcium carbonate. talc. attapulgite, montmorillonite. kiesclguhr. etc.) and ground synthetic minerals (e.g. highly dispersed'silicic acid. silicates. e.g. alkali silicates. etc. whereas the following may beehiefly considered for use ascoifventional carrier vehicle assistants, e.g. surface-active agents. for this purpose: emulsifying agents. such as nonionic'and- /or anionic emulsifying agents (cg. polyethylene oxide esters of fatty acids. polyethylene oxide ethers of fatty alcohols. alkyl sulfates. alkyl sulfonates. aryl sulfonates. etc.. and especially alkyl arylpolyglycol ethers. magne sium stearate. sodium ole-ate. etc.); and/or dispersing agents. such as lignin. sulfite waste liquors. methyl cellulose. etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/o with such solid and/or liquid dispersible carrieryeh icles. and/or with other knowncompatible active agents. especially plant protection agents such as other insecticides and acaricides. or rodenticides. fungicides, bacterieides. nematocides. herbicides. fertilizers, growthregulating agents. etc., if desired. or in the form of particular dosage preparations for specific application made therefrom. such as solutions. emulsions.suspensions.powders. pastes. and granules which are thus ready forusc.

As concerns commercially marketed preparations. these generally contemplate. carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1 95 71 by weight. and preferably 0.5-9()'/z by weight. of the mixture, whereas carrier composition mixtures suitable for direct applicationor field application generally contemplate those in whichthe active compound is present in an amount substantially between about 0.0001 1 preferably ().()ll'/(. by weight of the mixture. Thus. the present invention contemplatesover-all composi tions which comprises mixtures'of a conventional dispersihle carrier vehicle such as (l a dispersible inert finely divided carrier solid. and/or (2) a dispersiblc carrier liquid such as an inertorg'anic solvent and/or water preferable including a surface-active effective amount of a carrier vehicle assistant. e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 0.()()l957(. and preferably (HM-95%. by weight of the mixture. y

The active compounds can also be used in accor dance with the well known ultra-low-volume process with good success. i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same. via very effective atomizing equipment, in finely divided form. c.g. average particle diameter of from 50-1 ()0 microns, or even less. i.e. mist form. for example by airplane crop spraying techniques. Only up to at most about a few liters/hectai'e are needed, and often amounts only up to about l5 to 1000 g/heetare. preferably to 600 g/hectare. are sufficient. In this process it is possible to ,use highly concentrated liquid compositions with said liquid carrier vehicles containingfrom about 20 to about by weight of the active compound or even the active 6 substance alone, e.g. about 20-1007 by weight of the active compound.

Furthermore. the present invention contemplates methods of selectively killing. combating or controlling pests. e.g. insects and acarids. which comprises applying to at least one of correspondingly (a) such insects. (b) such acarids. and (c) the corresponding habitat thereof. i.e. the locus to be protected. a correspondingly combative or toxic amount. i.e. an insecticidally or acaricidally effective amount. of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner. for instance by spraying. atomizing. vaporizing. scattering. dusting. watering. squirting. sprinkling. pouring. fumigating. and the like.

It will be realized. of course. that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis. unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated. without limitation. by the following examples:

EXAMPLE 1 Myzus Test (contact actionj Solvent: 3 parts by weight acetone Emulsifier: l part by weight alkylarylpolyglycol ether Toproduce a suitable preparation of active compound. 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is di luted with water to the desired concentration.

C abbage plants Brusxicu ult'ruccu) which have been heavily infested with peach aphids Myzus persic'uv) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time. the degree of destruction is determined as. a percentage: 1007! means that all the aphids are killed whereas (l /r means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds. the evaluation times and the results can be seen from the following Table I:

Table l-continued Table 2-continued A,

(plant-damaging insects) Myus test ('oneentra- Active compounds tion of Degree of LlCS- active truction in 2 compound after 1 day CH l.

| lN,=CH-()C. ,H (3) 0.1 100 0.01 20 ("H CH P N=(HO(H;, Y 141 V 0.1 100 (Llll )(l (H 5 CH,.()\I

i P N=(1 -1 O(H.. 0.1 100 0.01 75 (H S H, O\( i1 PN ('H()(H 0.1 100 0.01 95 (H S EXAMPLE 2 Doralis Test (systemic action) Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable preparation of active compound. 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

Bean plants (Viriufulm) which have been heavily infested with the bean aphid (Doralisfilluw) are watered with the preparation of the active compound so that the preparation of active compound penetrates into the soil without wetting the leaves of the bean plants. The active compound is taken up by the bean plants from the soil and thus reaches the infested leaves.

After the specified period of time. the degree of destruction is determined as a percentage. 100% means that all the aphids are killed; 0% means that none of the aphids are killed.

The active compounds. the concentrations of the active compounds. the evaluation time and the results can be seen from the following Table 2:

Table 2 plant-damaging insects) Doralis test (syst. action) (plant-damaging insects) Doralis test (syst. action) Coneentra-' Active compounds tion of Degree of desactive truction in compound after 4 days CH O O 0.1 100 P-N=CHOCH:1 ().()l l ()0 0.001 (Tl-1 S C. H -,O O

v 4 0.1 PN=CH- OCH; (5) 0.01 100 (l.()()l l00 CH S EXAMPLE 3 Tetranychus Test/Resistant Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylarylpolyglycol ether To produce a suitable prepara'tion of active compound. 1 part by weight of the active compound is mixed 'with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Bean plants (P/iuseolus vul aris). which have a height of approximately 10-30 cm.. are sprayed with the prep-' aration of the active compound until dripping wet. These bean plants are heavily infested with spider mites (T(U't|!l \L'/lll.$' urticae) in all stages of development.

After the specified periods of time. the effectiveness of the preparation of active compound is determined by counting the dead mites. The degree of destruction thus obtained is expressed as a percentage: 100% means that all the spider mites are killed whereas 0% means that none of the spider mites are killed.

The active compounds, the concentrations of the active compounds. the evaluation times and the results can be seen from the following Table 3:

Table 3 The following further examples are set forth to illustrate. without limitation, the process for producing the active compounds according to the present invention.

EXAMPLE 4 7] g (0.5 mole) of Omethyl-S-methyl-thiolphosphorie acid ester amide are heated to the boil under reflux for 4 hours with 92 g of orthoformic acid ethyl ester. Subsequently. the alcohol formed is distilled off and the residue is distilled. There are obtained 56 g (57% of theory) of the desired N-(O.S-dimethylthiolphosphoryl)-iminoformic acid ethyl ester of the boiling point 84C/O.()l mm Hg and the refractive index n,, 1.4892. LD rat per os approximately 200 mg/kg.

EXAMPLE 5 47 g (0.3 mole) of O-ethyl-S-methyl-thiolphosphoric acid ester amide and 55 g orthformic acid ethyl ester are heated to 150C for 4 hours; the alcohol forming is distilled off simultaneously. The residue is distilled and there are obtained 52 g (82% of theory) of the desired N-( O-ethyl-S-methyl-thiolphosphoryl )iminoformic acid ethyl ester of the boiling point 88C/().()l mm Hg and the refractive index n,, 1.4802. LD rat per 0s 50 mg/kg.

EXAMPLES 6-l 0 Analogously to the compounds described above. there are prepared:

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation. and that various modifications and changes may he made without departing from the spirit and scope of the present invention.

What is claimed is:

l. A N-(O.S-dialkyl (thiono)-thiolphosphoryl iminoformic acid alkyl ester of the formula 4. The compound according to claim 1 wherein such compound I is N-( O-ethyl-S-methylthiolphosphoryl iminoformic acid ethyl ester of the formula 5. The compound according to claim 1 wherein such compound is N(O.S-dimethylthionothiolphosphoryl iminoformic acid ethyl ester of the formula 6. The compound according to claim 1 whcrcin such compound is N-(O,S-dimcth'lthiolphosphoryl imin oformic acid methyl ester of the formula 7. The compound according to claim 1 whcrcin such compound is N-(O-cthyl-S-mcthylthiolphosphoryl)- iminoformic acid methyl cstcr of the formula The compound according to claim 1 wherein such compound is N-(O.S-dimctliylthionothiolphosphoryl iminoformic acid methyl ester of the formula 9. A process for the production of a compound accordingto claim I in which an O,S-dialkyl-(thiono )-thiolphosphoric acid ester amide of the formula is reacted at a tcmpcraturc of about l()() to 200C with an ortho-formic acid alkyl ester of the formula 10. A compound of the formula. 

1. A N-(O,S-DIALKYLL (THIONO)-THIOLPHOSPHORYL)-IMINOFORMIC ACID ALKYL ESTER OF THE FORMULA
 2. A compound according to claim 1 in which R and R'' each has 1 to 4 carbon atoms and R'''' has 1 to 3 carbon atoms.
 3. The compound according to claim 1 wherein such compound is N-(O,S-dimethylthiolphosphoryl)-iminoformic acid ethyl ester of the formula
 4. The compound according to claim 1 wherein such compound is N-(O-ethyl-S-methylthiolphosphoryl)-iminoformic acid ethyl ester of the formula
 5. The compound according to claim 1 wherein such compound is N-(O,S-dimethylthionothiolphosphoryl)-iminoformic acid ethyl ester of the formula
 6. The compound according to claim 1 wherein such compound is N-(O,S-dimethylthiolphosphoryl)-iminoformic acid methyl ester of the formula
 7. The compound according to claim 1 wherein such compound is N-(O-ethyl-S-methylthiolphosphoryl)-iminoformic acid methyl ester of the formula
 8. The compound according to claim 1 wherein such compound is N-(O,S-dimethylthionothiolphosphoryl)-iminoformic acid methyl ester of the formula
 9. A process for the production of a compound according to claim 1 in which an O,S-dialkyl-(thiono)-thiolphosphoric acid ester amide of the formula
 10. A compound of the formula, 